Process of producting fast dyeings on cellulose esters and ethers and the dyed fiber obtained thereby



Patented May 27-, 1941 .UNITED STATES PATENT OFFICE PROCESS OF PRODUCING FAST DYEINGS ON CELLULOSE ESTERS AND ETHERS AND THE DYED' FIBER OBTAINED THEREBY Georg Kranzlein and Carl Josef Miiller, Frank-v fort-on-the-Main, and Werner Kirst, Konigstein in Taunus, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application November 9, 1939, Se-

rial No. 303,538. In Germany December 1,

Claims.

a coupling component, as for instance, 2.3-hydroxynaphthoic acid or beta-naphthol.

This invention relates to the production of fast dyeings on cellulose esters or ethers in a much simpler manner by applying to the cellulose ester or ether or dissolving therein an azo-dyestuff which does not contain a sulfonic acid group, but contains in the molecule an aminogroup capable of being diazotized and a free position capable of coupling with diazo-compounds, then diazotizing the compound and causing the diazo-compound obtained to combine with itself, if desired by adding to the diazo-bath an agent neutralizing the acid or having an alkaline action, after the diazotization is finished, or by passing the diazotized goods through a bath containing one of the said agents.

The azo-dyestuff may be applied to the fiber in an acid or neutral solution or suspension. The diazotization is performed by means of the usual agents. The azo-dyestufis may also be added to the spinning solution.

In comparison with the known process the new process is distinguished by its simple mode of application, since the after-treatment with a developer and, accordingly, a coupling bath with a separate coupling component can be dispensed with. Moreover, the fastness to wet-processing of the dyeings obtained by this invention is superior to that of the known dyeings obtainable by using a separate heterogeneous coupling com-- ponent.

The following example serves to illustrate the invention, but it is not intended to limit it thereto: 1 kilo of acetate silk yarn is treated for one hour at about 80 C. with a suspension containing in 25 liters of water grams of a finely dispersed azo-dyestuff having the following constitution:

NH2 (5.011s

(obtainable by coupling diazotized 1-amino-2- methoxyl-nitrobenzene in an acid medium with 2 amino 5 hydroxy naphthalene and subsequently reducing the nitro-group) The yarn is then rinsed and introduced into a bath containing in 30 liters of cold water 30 grams of sodium nitrite and cc. of concentrated hydrochloric acid. After one hour the diazotization is complete. The material is then centrifuged and the dyeing is'developed in a cold bath containing in 30 liters of water. 80 cc. of ammonia of 25 per cent strength. The goods are then centrifuged and dried. A black-brown dyeing of good properties of fastness, especially of very good fastness to wet-processing is obtained.

The following table indicates a number of other dyeings obtainable by this invention:

Parent component Shade acid I l l-amino-l-nitrobenzcne 2-aminot-hydroxynaphthalene, reduced,

or acid Brown-black. l-amino-4-acetylaminobenzene Z-aminm5-hydroxynaphthalene, saponified.

ac 2 1-amino-z-chloro-l-nitrobenzene -v 2-amino 5-hydroxynaphthalene, reduced Black-brown.

ac 3 1.4-diamino-3.5-dichlorobcnzcne 2-amino-5-hydroxynaphthalene Violet-brown.

aci 4 l-amino-3-nitro-6-methylbenzene 2-aminor5-hydroxynaphthalcna reduced Brown.

ac f 5 l-amino-l-nitro-o-methylbenzcne 2-amino-5-hydroxynaphthalcnc, reduced Violet-brown.

8C1 6 4nitro-4-aminodiphenylamine Z-amino-fihydroxynaphthalene, reduced Black.

7 l-amino-4-nitro-2-methoxy fi-chlorobenzene 2-amino-5 hydroxynaphthalene, reduced. Violet-black.

8 2-amino-5-hydroxynaphthalene m-amino-acetanili(lo Brown.

9 2-amino-S-hydroxynaphthalcne l-aminonaphtl alene Violet-brown. l0 2-aI3Inino-5-hydroxynaphthalcne aniline, according to the statements in German Patent Brown.

11 2-amino-5-hydroxynaphthalene 1-amino-3.5-dimethylbenzene D0. 12 2-amino-5-hydroxynaphthalene 1-amino-2-methoxy-5-methylbcnzene Do. 13 2-amino-8-hydroxynaphthalene r l-aminc2-methoXy-5-mcthylbenzcne Do.

Parent component Shade alkaline 4 2-amino-S-acetoxy-naphthaleue 2-a rnino-8-hydroxynaphthalene, saponified I Violet-black. l5 1-arnino-8-h%droxynaphthalene aniline, according to the statements in German Patent Brown.

No. 131 8 16 2 i -gihydroxynaphthalene i-aminonaphthalene Black-brown. 17 2-amino-8-hydroxynaphthalene i-amino-Bjfiimethylbcnze Brown. 18 2-amino-8-hydroxynaphthalene 3-am no-acetanilide Rcddish-brown. 19 2-amino-B-hydroxynapbthalene r l-arn no-2.5-dimethoxybenze 20 l-amino-5-hydroxynaphthalene l-am1no-2-methoxy-5-methylben Red-brown. 21 l-(3-aminophenyl)-3-methyl-5-pyrazol%ne l-aminonaphthalene Brown.

am 22 l-amino-4-nitro-2-methoxybenzene 2-amino-7-hydroxynaphthalene, reduced" Brown-black. 23 l-aminc-4-nitro-2-chlorobcnzene 1.3-dlhydroxybenzene, reduced Brown. '24 l-amino-4-nitro-2-methoxybenzene phenol, reduced 25 4-aminobenzoylacetylaminobenzene l-ammo-Zi-methoxybenzene Brown-orange, 26 Sulfurous acid ester of l-ammo-B-hydroxynaphth alene 2-amino-4-methoxy Brown.

benzene, saponifled.

ac 27 Aniline l-amincfrhydroxynaphthalene Red-brown.

ac 2s Aniline 2-arnino-5 hydroxynaphthal n Yellow-brown.

am 29 Aniline 1-amino-7-hydroxynaphthalcne Brown.

am 30 Aniline 2-amino-7-hydroxyna pht len Yellow-brown,

am 31 1-amino4-acetylaminobenzene d 2-8111 o-5- y o y aptha ene Brown-orange,

s01 32 1 i 3-gcety1amin0benzene a 2-amino-5-hydroxynaphthalene Orange-brown.

a 33 a ino.3.a etylaminobenz ene z-amino-ehydroxynaphthalene, saponitied Red-brown. 34 4-aminophenol 2am1no-4-metl1oxy-l-methylbenzene Coppepb own- 35 3-aminophenol l-naphthylaml Br 30 4-aminopl1enol l-naphthylaminc O1ive br0w-n 37 ni1 n phenol, reduced. Y llow-brown. 38 a i ine phenol, reduced Brownish-yellow. I 9 4-nin-oaniline 1.5-naphthylenedlamm Brown- 40 2-nitro-4-niethoxy-l-aminobenzene 1.5-naphthy1ened am ne Do, 41 2-nitro-4-methoxy-l-aminobenzenu 1.5 naphthylenedmmme, reduced acid 42 3-nitroauiline 1-amino-7-hydroxynaphthalene, reduced,

or Do. l-amino-3-acetylaminobenzene l-arnino-7-hydroxynaphthalenc, saponificd.

- am 43 4-nitroanilinc i 1-arnino-7-hydroxynapbthalene, reduced,

ac Red-brown. l-amino-l-acetylaminobcnzene lacmmM-hydroxynaphthalene, sapomfied.

8.01 44 p n in -2. %];oxy4-nitrobenzene l-amino-7-l1ydr xyn ph alen r uced D0. 45 Z-aminoahydroxynaphthalene 1-am no-2-rnethyl-5-methoxybenzene Brow-m 4G 2. ino 5-h d o ynaphthalene l-ammoa-met oxy-fi-m t yl nz n Violet-brown.

01 47 1.a i 4.nitro-2-chlorobenzene z-amino-ahydr xynap t n Brown-orange. 48 3-nitroaniline 1.3-dihydroxybcnzene, reduced 49 4-nitroaniline LB-dihydroxybenzcne, reduced Violebbrowm 50 4-nitro-2.5-dimethoxy-4-aminoazobenzcne -r 1.3-d1hydroxybenzcne, reduced R d. 51 aniline LS-diaminobenznc Brown. 52 B-nitroaniline 1.3-diaminobenzene, reduced,

or Red-brown. l-amino-3-acetylaminobenzene -v 1.3-diam nobenzenc, sapomfied. 53 amitmanmne z-methyl-fi-metholiy-l-a Brown- 54 S-nitroaniline v 2.4-dimcthyl-l-am1nobenzene y n n 55 Bismarck brown Do 56 2-nitroA-amino-l-methylbenzene Lfi-naphthylenediammc B 57 3.3minophenol Luv-aminophenyl)-3-methyl- -DyrM Orange.

We claim:

1. The process which comprises applying to fibrous material of the group consisting of cellulose esters and ethers a mono-azo-dyestufi which does not contain a sulfonic acid group, but contains in the molecule an amino-group capable of being diazotized and a free position capable of coupling with diazo-compounds, then diazotizing the compound on the fiber and causing the diam-compound obtained to combine with itself by an alkaline treatment.

2. The process which comprises applying to fibrous material of the group consisting of cellulose esters and ethers a mono-azo-dyestufi which does not contain a sulfonic acid group, but contains in the molecule an amino-group capable of being diazotized and a free position capable of coupling with diazo-compounds, then diazotizing the compound on the fiber and causing the diazo-compound obtained to combine with itself by passing the diazotized goods through a bath having an' alkaline action subsequently to the diazotization process.

3. The process which comprises applying to cellulose esters the azo-dyestufi obtainable by coupling diazotized 3-aminopheno1 with 1-(3'- aminophenyl) 3 methyl 5 pyrazolone, then diazotizing the azo-dyestufi on the fiber and causing the diazo-compound obtained to combine with itself by an alkaline treatment.

4. The process which comprises applying to cellulose esters the azo-dyestuif obtainable by coupling diazotized l-anlinol-acetylaminobenzene in an acid medium with 1-amino-7-hydroxynaphthalene and subsequently splitting of! the acetyl-group by saponification, then diazotizing the azo-dyestuff on the fiber and causing the diazo-compound obtained to combine with itself by an alkaline treatment.

5. The process which comprises applying to cellulose esters the azo-dyestuff obtainable by coupling diazotized 3-amino-phenol with 1- naphthylamine, then diazotizing the azo-dyestuff on the fiber and causing the diazo-compound obtained to combine with itself by an alkaline treatment.

' 6. Fibrous material of the group consisting of cellulose esters and ethers dyed with an azo-dyestuff obtainable on the fiber by the process claimed in claim 1.

'7. Fibrous material of the group consisting of cellulose esters and ethers dyed with an azo-dyestufi obtainable on the fiber by the process claimed in claim 2.

8. Cellulose esters dyed with an azo-dyestui! 10. Cellulwe esters dyed; with an azo-dyestufl obtainable on the fiber by the process claimed in obtainable n the r y the P o s med claim 3. in claim 5.

9. Cellulose esters dyed with an azo-dyestuflf GEORG KRKNZLEIN- obtainable on the fiber by the process claimed 5 CARL JOSEF mum, in claim 4; I WERNER ms'r. 

